The Desulfurization of Mercaptans With Trialkyl Phosphites

Hoffmann, Friedrich W.; Ess, Richard J.; Simmons, Thomas C.; Hanzel, Robert S.

doi:10.1021/ja01605a034

Cited by 88 publications

(49 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[14] Soon thereafter, in a key advance, Walling and Rabinowitz put forth a proposed mechanistic sequence, wherein an alkylthiyl radical adds reversibly to phosphite, thereby generating an intermediate phosphoranyl radical. [15] Subsequent b scission was envisioned to provide an alkyl radical, and rapid hydrogen abstraction from the parent thiol would furnish the product alkane, thereby serving to propogate the chain (Scheme 1).…”

mentioning

confidence: 99%

Free‐Radical‐Based, Specific Desulfurization of Cysteine: A Powerful Advance in the Synthesis of Polypeptides and Glycopolypeptides

2007

View full text Add to dashboard Cite

Being specific: The specific conversion of Cys (seleno‐Cys) into Ala by a free‐radical‐mediated reduction can be achieved in an aqueous medium under mild conditions (see scheme, PG=protecting group). The conversion can be achieved in the presence of all 20 natural amino acids as well as a range of functional groups. This native chemical ligation followed by the Cys into Ala conversion will enable the synthesis of complex peptides and glycopeptides.

show abstract

mentioning

confidence: 99%

Free‐Radical‐Based, Specific Desulfurization of Cysteine: A Powerful Advance in the Synthesis of Polypeptides and Glycopolypeptides

2007

View full text Add to dashboard Cite

show abstract

“…After taking note of a 1956 disclosure by Hoffmann describing a desulfurization reaction between mercaptan and trialkylphosphite,lviii in a totally different context, we explored the use of trialkylphosphines, in particular TCEP, to effect a cysteine reduction lix. TCEP was an attractive choice for several reasons.…”

Section: Resultsmentioning

confidence: 99%

Recent departures in the synthesis of peptides and glycopeptides

Kan

Danishefsky

2009

Tetrahedron

View full text Add to dashboard Cite

In this account, we describe the results of a research program directed to the proposition that chemical synthesis can play a valuable role in identifying biologic level molecules worthy of pharma level development. We recount our journey towards the chemical synthesis of homogeneous erythropoietin, the challenges we encountered, and our efforts to address deficiencies in the current "state of the art" of glycopeptide synthesis. Here we describe new methods for the synthesis of glycopeptides that have emerged from the erythropoietin adventure, including the development of unique C-terminal acyl donors, novel amide bond forming methods, and new ligation and coupling strategies.

show abstract

“…To this end, Danishefsky and coworkers turned to a radical-promoted desulfurization method [72] based on an initial report by Hoffman et al 50 years earlier on the desulfurization of thiols, under thermal or photochemical conditions, in the presence of trialkylphosphites [73]. The subsequent use of trialkylphosphines to promote desulfurization was also reported [74].…”

Section: Ligation-desulfurizationmentioning

confidence: 99%

Modern Extensions of Native Chemical Ligation for Chemical Protein Synthesis

Malins

Payne

2014

Protein Ligation and Total Synthesis I

View full text Add to dashboard Cite

Over the past 20 years, native chemical ligation has facilitated the synthesis of numerous complex peptide and protein targets, with and without post-translational modifications, as well as the design and construction of a variety of engineered protein variants. This powerful methodology has also served as a platform for the development of related chemoselective ligation technologies which have greatly expanded the scope and flexibility of ligation chemistry. This chapter details a number of important extensions of the original native chemical ligation manifold, with particular focus on the application of new methods in the total chemical synthesis of proteins. Topics covered include the development of auxiliary-based ligation methods, the post-ligation manipulation of Cys residues, and the synthesis and utility of unnatural amino acid building blocks (bearing reactive thiol or selenol functionalities) in chemoselective ligation chemistry. Contemporary applications of these techniques to the total chemical synthesis of peptides and proteins are described.

show abstract

The Desulfurization of Mercaptans With Trialkyl Phosphites

Cited by 88 publications

References 0 publications

Free‐Radical‐Based, Specific Desulfurization of Cysteine: A Powerful Advance in the Synthesis of Polypeptides and Glycopolypeptides

Free‐Radical‐Based, Specific Desulfurization of Cysteine: A Powerful Advance in the Synthesis of Polypeptides and Glycopolypeptides

Recent departures in the synthesis of peptides and glycopeptides

Modern Extensions of Native Chemical Ligation for Chemical Protein Synthesis

Contact Info

Product

Resources

About